Hierarchically Structured Stimuli-Responsive Liquid Crystalline Terpolymer–Rhodamine Dye Conjugates

Optically responsive materials are applied in sensing, actuators, and optical devices. One such class of material is dye-doped liquid crystal polymers that self-assemble into cholesteric mesophases that reflect visible light. We report here the synthesis and characterization of a family of linear an...

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Bibliographic Details
Main Authors: Samiksha Vaidya, Meenakshi Sharma, Christian Brückner, Rajeswari M. Kasi
Format: Article
Language:English
Published: MDPI AG 2025-01-01
Series:Molecules
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Online Access:https://www.mdpi.com/1420-3049/30/2/401
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Summary:Optically responsive materials are applied in sensing, actuators, and optical devices. One such class of material is dye-doped liquid crystal polymers that self-assemble into cholesteric mesophases that reflect visible light. We report here the synthesis and characterization of a family of linear and mildly crosslinked terpolymers prepared by the ROMP of norbornene-based monomers. The three monomers were composed of (i) rhodamine dye through one or two norbornene end groups utilizing flexible C<sub>10</sub>-alkane spacers, (ii) a cholesteryl liquid crystal (LC) using C<sub>9</sub>-alkane spacers, and (iii) PEG side chains. We investigated how these architectural variations in these terpolymers impacted their hierarchically self-assembled mesophase properties. We probed their composition, morphology, thermal, mechanic, photochromic, and mechanochromic properties using, inter alia, <sup>1</sup>H NMR spectroscopy, DSC, temperature-dependent SAXS, diffuse reflectance UV-vis spectroscopy, and optical polarization microscopy. The new terpolymers exhibited architecture-dependent thermochromic, mechanochromic, and piezochromic properties arising from LC–rhodamine dye interactions. We found that a compromise between the rigidity and flexibility of the terpolymer architectures needed to be stricken to fully express stimuli-responsive properties. These terpolymers also showed distinctly different properties compared to those of a previously reported structurally related liquid crystalline copolymer made from two monomers. These findings help to define the design principles for optimally stimuli-responsive liquid crystalline polymers.
ISSN:1420-3049